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Chapter 1
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Agro-Wastes-Based Feedstock asaSource
forBionanomaterials Production:
Outcomes andChallenges
PoojaSankaranarayanan, T.A.Anboli, andT.V.Suchithra
Abstract Nanotechnology has notably impacted science and technology over
recent years, especially in medicine, electronics, food safety, and energy. Using
nanomaterials in agriculture has addressed several issues, such as crop protection,
soil management, and post-harvest treatment. Literature reports suggest the use of
nanotechnology in farming increases the nutrient uptake of soil. The positive outcomes of nanofertilizers, nanopesticides, and nanosensors led to further experimentation of nanomaterials in agriculture-based applications. Second-generation biofuel
production from agro-wastes ignited the curiosity of developing bionanomaterials.
The emergence of structured nanomaterials such as nanobers, nanocellulose, and
nanoporous membranes led to several applications in nano-based product synthesis.
Nanocatalysis, nanosensors, smart nanoparticle delivery, and nanomaterials in
nutrient uptake were some of the recent applications of nanotechnology in precision
agriculture. Most of the synthesized bionanomaterials were found to have medicinal
value, especially those that use zinc, iron, silver, and gold as precursors. The critical
question lies in the potential toxicity of nanoparticles in the environment, which is
still unanswered. In short, this chapter lists the possible sources for bionanomaterials production concerning their commercial applications. Despite having a greater
scope in agriculture, bionanomaterials production from agro-wastes holds an upper
hand due to its easy availability and reduction potential. If the toxicity of the nanomaterial is adequately addressed, the choice of agro-wastes as a precursor in developing bionanomaterials may improve the commercial viability of green synthesis.
Keywords Nanotechnology · Bionanomaterials · Agro-wastes · Nanocatalysis ·
Nanoparticles · Toxicity
P. Sankaranarayanan · T. A. Anboli · T. V. Suchithra (*)
School of Biotechnology, National Institute of Technology, Calicut, Kerala, India
e-mail: drsuchithratv@nitc.ac.in
Ltd. 2024
S. Bose et al. (eds.), Concepts in Pharmaceutical Biotechnology and Drug
Development, Interdisciplinary Biotechnological Advances,
https://doi.org/10.1007/978-981-97-1148-2_1
3© The Author(s), under exclusive license to Springer Nature Singapore Pte
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P. Sankaranarayanan et al.
1.1 Introduction
Nanomaterials have greater scientic signicance owing to its smaller size, higher
surface area, and unique morphological properties than conventional bulk particles.
Nanoparticles (NPs) are mainly composed of three layers: surface, shell, and core.
The method of synthesis decides the physical nature and application of nanomaterials. Methods used to prepare nanoparticles are mechanical grinding, laser ablation,
electro-explosion, chemical vapor deposition, sol-gel synthesis, ultrasound-assisted
synthesis, colloid nanoparticles synthesis, and green synthesis (Sasidharan et al.
2019). Out of all physical and chemical synthesis approaches, green synthesis has
several advantages: low cost, simple and eco-friendly synthesis, and low energy
requirements. As the name suggests, green synthesized nanoparticles get their
“nano” form sculpted from plants’ “green” elements, namely antioxidants, avonoids, and phenolic compounds, which act as capping and reducing agents. There
are various reviews on the use of plant precursors in developing nanoparticles with
medical and non-medical applications. Some applications of nanoparticles are
detailed in Table1.1.
Advancement in the eld of material sciences and a better understanding of
remedial properties of plant-based nanoparticles resulted in improvised mechanisms of synthesis, thereby focusing on targeted applications (Zangeneh and
Zangeneh 2020). Metallic nanoparticles like Gold (Au), Zinc (Zn), Silicon (Si),
Silver (Ag), and Cerium (Ce) nanoparticles have several applications in the eld of
medicine, agriculture, textile, micro-electronics, food processing, and industry
(Ngu et al. 2016). Simultaneously, carbon-based nanomaterials from plants have
introduced the cost of practical fabrications to the electronics sectors in the form of
fullerenes, carbon nanotubes, quantum dots, and graphene oxides (Jamdagni etal.
2018). The low-cost synthesis and power-saving nature of these fabrications paved
the way to develop “nanoelectronics” and lifted nanotechnology to a greater height.
Using silicon and carbon nanoparticles from agricultural wastes as catalysts in
the production of biofuels has reduced production costs by incorporating cheaper
enzyme immobilization techniques in heterogenous catalysis (Hazmi etal. 2020).
Nanocellulose from lignocellulosic biomass has raised the standards of ber-based
engineering applications. The richer content of brous materials in plant sources led
to the development of many nanocomposites and nanodesigns, which can be used as
nanofertilizers, nanosensors, nanopesticides, and even in improving soil fertility by
increasing its nutrient content. Though nanobiomaterials possess fascinating applications and advantages, several issues leading to its toxic environmental impact
were also expressed (Prasad etal. 2017).
Most of the produced nanomaterials are usually studied for its medicinal
properties rather than its industrial outcome. Developing nano-based fertilizers,
detergents, and sensors exposed the scope of agricultural and industrial applications in nanotechnology. For example, cost-efcient natural detergents from
1 Agro-Wastes-Based Feedstock as a Source for Bionanomaterials Production…
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Fan etal.
Khraisheh
etal. (2013)
absorbent in removing
carbamazepine
Shrestha etal.
(2019)
Adsorbent materials in
water puriers
adsorption property
Wang etal.
(2016)
High photocatalytic
activity, potential in
wastewater treatment
Highest photodegradation
efciency in removal of
methyl orange during
(2018)
Can be used as
insulating agents
Exhibit superior sound-
absorption property
photocatalytic experiment
(2017)
Nanopesticide Sujitha etal.
Anopheles stephensi and A.
sundaicus
Nanoinsecticide Khoshraftar
etal. (2019)
Fungistat Huang etal.
Myzus persicae
5
(continued)
(2020)
fungicide, epoxiconazole
Average
size Shape Outcomes Applications Reference
Nanomaterials Mechanism/source
Table 1.1 Applications of Bionanomaterials from agro-wastes
15nm – Photocatalytic absorbent Can be used as
Calcination and chemical
coconut shell
2
Chemical synthesis
TiO
– – Iodine and methylene blue
followed
2
pretreatment methods for
coconut shells
Multi-step chemical reduction
process of rice husk using
KOH, NaOH, ZnCl
nanocomposite
Nanoporous carbon
materials
shape
15nm Tube-like
by carbonization
Modied sol-gel synthesis
using tetrabutyl titanate
-
2
Multi-walled carbon
nanotubes—TiO
53.2nm –
bamboo leaves, followed by
loaded
nanocomposite
Cellulose nanobers Chemical pretreatment of
Spherical Anti-malarial activity against
<
100nm
380nm Spherical Insecticidal activity against
ultra-sonication process
Valoniopsis pachynema algae
Biological synthesis
CdS nanopesticides Green synthesis from
Eucalyptus globulus extract
Nanocapsules Green synthesis from
13nm Spherical Exhibit synergistic action with
lucidum leaf extract
Ag nanoparticles Green synthesis from Ligustrum
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P. Sankaranarayanan et al.
(2016)
Catalyst Prasad etal.
and used as a catalyst in the
Average
size Shape Outcomes Applications Reference
2–20nm Spherical Excellent magnetic property
Yuvakkumar
Antimicrobial and free
preparation of 2-oxo-1,2,3,4-
tetra hydropyrimidine
Antibacterial activity against
104nm Face-centered
etal. (2014)
radical property
Staphylococcus aureus and
Escherichia coli
crystalline
lattice
(2014)
Catalytic property Liang etal.
Reduces 4-nitrophenol to
4-aminophenol
shape with a
3.81nm Spherical
porous nature
Green synthesis from
watermelon rinds
4
O
3
Nanomaterials Mechanism/source
Magnetic
Table 1.1 (continued)
Fe
Green synthesis from
Nephelium lappaceum L.
(Rambutan) peel extract
nanoparticles
Nickel oxide
nanocrystals
to form AgNPs through
3
chemical pretreatment followed
by green synthesis
eggshell is used to reduce
AgNO
Chem-biosynthesis
Ag nanoparticles The extracellular matrix of the
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corn cobs with fewer chemicals have gained attention due to its fascinating
properties (Liu etal. 2020a). Similarly, bionanomaterials in pest control and dye
degradation are not much surprising due to its inbuilt antimicrobial nature
(Prasad etal. 2017). Ag and Au nanomaterials always synergize well in antimicrobial and photocatalytic applications (Liu etal. 2020b). Even though several
works have been discussed on plant sources and their material synthesis, a
detailed view of the source-based outcomes is essential. This chapter mainly
focuses on the most fascinating nanomaterial outcomes from different agricultural sources and their applications in various elds to give an outlook in this
sector. Certain limitations and misconceptions dealing with this technology
have also been intimated.
1.2 Nanomaterials fromHusk andShell Waste
Applications of bionanomaterials synthesized from fruit, leaf, ower, and seed
wastes were illustrated in Fig.1.1.
Fig. 1.1 Schematic representation of bionanomaterials synthesized from agro-wastes and their
applications
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P. Sankaranarayanan et al.
1.2.1 Rice Husk
Rice husk (RH) is a biodegradable and brous-rich biomass generated during rice
milling. It is rich in 50% cellulose, 25–30% lignin, 15–20% silica, and 10% moisture.
RH has applications in dye degradation, cement processing, etc. Some recent bionanomaterials produced from RH and their industry-oriented outcomes are listed
below. Carbon nanoparticles with an efcient quenching effect had been synthesized
from RH using the thermal-assisted acid-carbonization method, which can be an
alternative to existing uorescent dyes due to its cheaper production costs and lesser
toxicity (Ngu et al. 2016). Production of high-yield silicon dioxide nanoparticles
from acid-treated RH ash in a two-step process yielded almost 93.4%. Also, it does
not produce CO2 or any other toxins, and the method is cost-effective due to using
Na2CO3. The morphological and compositional characteristics of the produced
SiO2NPs were in par with the commercial silica, thereby expanding its applications
in the eld of microelectronics (Nayak and Datta 2020). RH ash is highly utilized in
biodiesel and biomethane production due to its textural properties and thermal stability. For instance, a nano-bifunctional supermagnetic catalyst which is produced from
RH char through K2O doping wet impregnation method yielded a maximum of 98.6%
of biodiesel from used cooking oil by using 4wt% of catalyst, and it can be reused up
to 5 times, without compromising its catalytic efciency (Hazmi etal. 2020).
1.2.2 Coconut Shell
Coconut shell, a typical domestic waste in countries like Indonesia and India, is
considered a cheaper source for production of charcoal. Applications of coconut
shells include water purication, manufacturing of mosquito coils and incense
sticks, etc. The coconut shell-based activated carbon in carbon nanotubes matrix
can be used as an innovative capacitive deionization electrode for desalination
applications. This electrode composite showed good cyclic stability with low energy
consumption than the commercial ones (Huynh et al. 2020). Due to its brous
nature, coconut shell waste is reduced using the Hummers method to produce graphene oxide, with structural and textural properties of natural graphite, and has a
bandgap energy value of 4.38eV, which can be used for semiconductor applications
(Sujiono etal. 2020).
1.2.3 Egg Shell
Several studies reveal that the eggshell particles have 95% calcium carbonate and
5% inorganic components, making it a potential raw material for calcium-based
nanoproducts. Calcium oxide nanomaterials from eggshell waste can be chemically
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synthesized using sol-gel method, which involves less temperature, alkaline additives and relatively cheaper than other chemical methods (Habte etal. 2019). Both
nano-calcium oxide and calcium carbonate from eggshell have several applications
in water treatment, automobile, and paper industry. Eggshell also has medicinal
applications such as treatment of osteoporosis and in bone grafts. Calcium nitrate
from eggshell wastes had been chemically treated to produce diopside powders,
with which Poly (methyl methacrylate) was reinforced to make it a porous scaffold.
This porous nanocomposite’s mechanical and surface scaffolding assists in the biomedical eld (Choudhary etal. 2020).
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1.2.4 Walnut Shell andHusk
Walnut husks and shell pigments were believed to be a good resource for making
fabric dyes and inks in Rome and Europe. Metal nanoparticles from various parts of
the walnut tree have antimicrobial and antiradical applications. Iron oxide nanoparticles from walnut husk using a two-step co-precipitation method were investigated
for their cytotoxic activity on mouse embryonic broblast cell lines and human
colorectal adenocarcinoma cell lines. The cubic-shaped nanoparticles showed no
toxicity on the cell lines up to 1000μg/mL, making them suitable candidates for
drug-related applications (Izadiyan et al. 2020). Walnut has excellent adsorbent
capacity towards heavy metal ions, dyes, and organic compounds. Juglone dye
extracted from walnut shell powder can be used as reducing and capping agents for
the synthesis of Ag nanosols and nanodisks. Juglone has antimicrobial and antioxidant activity, enhancing the AgNPs’ properties. Meanwhile, the addition of cetyl
trimethyl ammonium bromide in nanoparticles resulted in micellar formation, hinting it as a potential surfactant (Zaheer 2019). The electrical potential of walnut shell
is less explored, despite having high cellulose content. Liquefaction is used to obtain
maximum cellulose from walnut shells, followed by the electrospinning process
resulting in carbon nanober mats. Thinner micropore structure with higher specic
surface area (408m2/g) was found to be a suitable electrode in lithium-ion batteries.
Charge capacity of 150 mAh/g with excellent cyclic stability till 100cycles proved
it to be a sustainable electrode for batteries (Tao etal. 2017).
1.3 Bionanomaterials fromCorn Cob
Metal nanoparticles and their antimicrobial activity have been closely examined
for decades. Very recently in 2020, AgNPs from corn cob were found to be a potential antiparasitic agent against Trypanosoma cruzi. Corn cob is used as bioreductant
along with AgNO3 to produce nano xylan. Characterization of nanoparticles
showed that nano xylan contains 81% xylan and 19% Ag. 100μg/mL of nano xylan
effectively eliminated 95% of parasite, which is considered a safer therapeutic
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alternative to benznidazole. In vivo study regarding the same is required to prove
its therapeutic efciency (Brito etal. 2020). Though eco-friendly products have a
low yield, replacement of waste biomass conversion is fast and reliable. Replacing
synthetic detergents with natural ones requires different approach to improve
cleaning capacity. There was a recent study on a three-step cellulose nanospheres
production process from corn cobs which can improve the cleaning capacity by the
mechanism called Pickering emulsions. The nanospheres’ life cycle assessment
and biocompatibility studies proved it to be a recyclable detergent (Liu et al.
2020a). Use of organic fertilizers was found to impart higher nutrition content to
the soil. Corn cob’s biochar impregnated with macro (N, Mg, Ca, K, P) and micronutrients (Na, Zn, Fe) made into nanocomposites enhances plant growth by preserving nutrients for a long time by keeping the typical properties of slow releasing
nanofertilizers such as water absorbance, salt index, retention and release abilities
(Lateef etal. 2019).
P. Sankaranarayanan et al.
1.4 Bionanomaterials fromFruit Waste
1.4.1 Citrus Peel Waste
The successful development in the green synthesis of nanoparticles is a great cause
for signicant hike in the applications of nanoparticles in the eld of medicine. Au
and AgNPs from fruit wastes have shown good stability at higher temperature and
pressure. In addition to this, ZnONPs synthesized from fruit wastes have several
applications in food packaging. A remodeled traditional approach can be taken by
using an aqueous orange peel extract as a reducing agent to produce ZnONPs from
Zinc acetate dihydrate. The minimal use of toxic chemicals and the catalytic capability of orange extract inuence the microstructural stability of ZnONPs. Orange
(Citrus sinensis) peel-based ZnONPs exhibit high bactericidal activity against
E.coli and S. aureus at a concentration of 0.025mg/mL, by interacting with the
microbes via the cell membrane and damaging DNA (Doan Thi etal. 2020). Similar
extraction technique is used to synthesize TiO2NPs using lemon (Citrus limon)
peel aqueous extract and titania powder. Hesperidin present in lemon peel extract
releases aglycone, which acts as capping and reducing agents for spherical TiO2NPs
and it is found to be free from contamination, unlike commercial ones. The photolytic ability of TiO2NPs was 70% more efcient than previously reported ones
(Nabi et al. 2020). Grapefruit (Citrus paradisi) peel-based distillate mixed with
1mM AgNO3 and reduced via the microwave-assisted sol-gel method for biosynthesizing AgNPs with an average size of 14.84nm is found to have a broad-spectrum antibacterial potency against E.coli, S. aureus, and Klebsiella pneumonia with
minimum inhibitory concentrations of 40, 20, and 40μg/mL, respectively (Ayinde
etal. 2019).
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1.4.2 Banana Peels
Banana peel is a well-known agricultural waste for green synthesis due to its higher
starch content. Au and Ag nanoparticles synthesized from banana peels have anticancer and antioxidant properties owing to their bioactive compounds. Au-dendrite
nanocomposites derived from banana peel possess the ability to reduce chloroauric
acid via hydrothermal routes (Liu etal. 2020b). It also has good biocompatibility,
antimicrobial and anticancer potency. Besides, it has proven to have an efcient
inhibitory effect on breast cancer cells at a concentration of 200μg/mL, with the
expense of a limited amount of chemicals. An invivo study conducted in nude mice
proved that support of infrared light in Au-dendrite nanomaterials suppressed tumor
growth and migration (Liu etal. 2020b). Rich potassium content in banana peels
can improve soil fertility. Shredded banana peel slurry mixed with potassium
hydroxide was ltered, in which urea and citric acid were added and homogenized.
The obtained nano mixture showed greater germination efciency in the rst planting week of tomato and fenugreek, thereby acting as a biostimulant in promoting
seedlings growth performance (Hussein etal. 2019).
1.4.3 Fruit Juices
Nanomaterials obtained from fruit waste-mediated synthesis have various biological
and engineering applications. CeO2NPs preparation from cerium nitrate requires
watermelon juice as a reducing agent. The simple solution combustion method followed by the calcination technique integrates the production of cubic-phase nanoceria.
Photocatalytic experiments on synthesized CeO2 nanomaterials showed degradation of
about 98% methylene blue dye in the presence of UV irradiation. Antibacterial activity
against K. aerogenes and S. aureus was also tested and maximum zone of inhibition
was observed at 50 and 100μL concentration respectively (Reddy Yadav etal. 2016).
Solar-assisted ZnO nanoparticle was prepared using lime juice as a reducing and capping agent with zinc acetate dihydrate as a precursor. Citric acid content in lime juice
reacts with zinc acetate to form zinc citrate, which further undergoes calcination to
form zinc oxide. Solar energy-assisted green synthesis mechanism contributes to the
crystalline nature of nanomaterials. But the presence of ascorbic acid in lime juice
greatly denes the size of ZnO nanoparticle (Hinge and Pandit 2017). Studies regarding its biological efciency and engineering applications were still under progress.
1.5 Bionanomaterials fromLeaf Wastes
Green synthesis based on leaf extract marked the beginning of nano era in industrial
applications. Impressive outcomes on energy conversion using leaf ash in heterogenous catalysis paved a way to extend its applications in biotechnology and its allied
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sectors. Bamboo ash, which contributes 70% of amorphous silica, has its applications as llers, medical additives, carriers, and composites. One such outcome is the
synthesis of SiO2NPs from bamboo leaf ash via thermal combustion and alkaline
extraction technique, making it a suitable ller for Polydimethylsiloxane (PDMS)
membranes. Pure PDMS membranes vs PDMS incorporated with SiO2 nanomaterials were analyzed for its pervaporation ux and thermal stability. A decrease in
contact angle increases the selectivity of membranes which was studied using acetic
acid-water mixture. The results proved that using Si-nanomaterials in PDMS
decreases the contact angle, thereby improving its thermal stability and evaporation
ux (Sethy etal. 2019). AgNPs and their antibacterial potency are well known for
ages. AgNPs obtained from tomato (Solanum lycopersicum) leaves were entrapped
in chitosan to transform them into Ag-chitosan nanoparticles through ion gelation.
In vitro and invivo evaluation of Ag-chitosan nanoparticles against Ralstonia sola-
nacearum, a plant pathogen, was carried out. The presence of Ag and chitosan
showed greater microbicide activity against pathogen within 48hrs. In-depth understanding of Ag-chitosan nanoparticles in the environment as well as eld study is
required to analyze the potential use of nanocomposites as a targeted fertilizer.
Zinc-based nanomaterials have unique structural and functional characteristics due
to its vast availability in natural precursors (Santiago etal. 2019). Nelumbo nucifera
(lotus) leaf extract was mixed with zinc nitrate in solution combustion approach to
produce ZnONPs. The produced ZnO NPs, when fabricated with poly
(3- hexylthiophene-2,5-diyl) (P3HT) in p-type organic eld-effect transistor (OFET),
shows prominent sensitivity for CO gas with eld-effect mobility of 10−2cm2/V/s.
The novelty of this approach lies in its eco-friendly synthesis and its capability to
function in open air. Optimization of electrical parameters such as eld-effect
mobility, on and off current values enhances the performance of CO adsorption. The
CO adsorption is dictated by the physical characteristics of active receptor layer
(ZnO NPs) and conducting properties of P3HT (channel layer). The use of natural
synthesized ZnO NPs in OFETs has greater signicance over commercially available transistors due to their purity and reusability (Narayana etal. 2020). Such transistors can extend its application in real-time air quality examinations, medical
diagnosis, and in nano forms of modulated electronics. Potential use of leaf ash as a
catalyst enhancer for biofuel synthesis was also investigated, but its signicance
over other biological ash (rice husk ash) in terms of performance as well as productivity has to be reviewed.
P. Sankaranarayanan et al.
1.6 Bionanomaterials fromFlowers
Flower extract is one of the recent sources in green synthesis of nanomaterials. Ag
nanomaterials obtained from plant extracts have shown antibacterial and antifungal
activity. Very few reports of ower extract-based nanomaterials having potential
applications in health care and industry were found. Aqueous extract of Allamanda
cathartica (Golden trumpet) mixed with AgNO3 solution incubated in the dark for
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